Non-alcoholic aerosol film forming compositions



3,100,179 N ON-ALCOHQLIC AEROSUL FELM FQRMING CQMPQSITIGNS William M. Perry, Bethlehem, Pa, assignor to General Aniline & Film Corporation, New York, N.Y., a corporation of Delaware No Drawing. Filed Mar. 13, 1950, Ser. No. 800,097

Claims. (Cl. 16787.1)

The present invention relates to non-alcoholic aerosol film forming compositions and particularly to improved hair waving and setting compositions.

There are numerous preparations available for the Waving and setting of human hair. Most of them are based on aqueous film forming solutions. The principal ingredient of such solutions is either a natural gum or resin or synthetic resins which upon evaporation of the liquid medium deposits a film or coating. In addition to natural gums and resins, various alcohol soluble proteids, such as gliadin, zein, and the like, gelatin, l3. mixture of egg albumen, casein, and sodium silicate, inorganic resinous compounds obtained by treating anhydrous monosodium phosphate with borax, and various water soluble polymeric [acrylic acid derivatives have been employed.

"Since natural gums, such as, for example, karaya gum, salts of alginic acid, gum acacia, etc., flake oil, dry hard, and impart an undesirable stiffness and brittleness, their use has been replaced by water soluble syntheticresins, such as those obtained by incomplete saponification or hydrolysis of polymeric acrylic and a-alkacrylic esters and amides. The disadvantage of waving fluid or hair dressing preparations containing such resins is that the preparations cannot tolerate bleaching agents Without the presence of ammonia, or an ammonium salt, such as ammonium carbonate. The latter compounds have the tendency to impart hydroscopicity to the resinous film or coating after evaporation of the liquid medium or carrier. As a result, the film or coating becomes tacky and develops a greasy feel. Moreover, depending upon the nature of the Water soluble polymeric acrylic acid derivative, some derivatives have the tendency of rubbing loose and falling ofi the hair in the form of small flakes resembling dandruff, while others require alkaline media for easy removal from the hair. It is well recognized among hair stylists and beauticians that ammonia has distinct hair stiffening characteristics whereby the fibers of the hair are attacked with a subsequent alterning of its natural life.

Alcoholic solutions of shellac have also been employed and are currently sold in limited amounts in a Freon system. The disadvantage of shellac is that it must be solubilized with alkaline media, such as caustic soda or caustic potash for preparation of the solution prior to formulation in a pressurized can. Moreover, the same alkaline media must be employed to remove it from the hair.

Various synthetic polymers have been tried for use in hair grooming preparations, but have not been practical because of their solubility characteristics, i.e., they are not suitable for application and/or removal from the natural hair filaments. For example, gums and many polymers are not soluble in aersol propellants and hence cannot be used in aersol sprays. Also, many polymers are affected by changes in the relative humidity and the hair varies from a stifi, boardy feed to a sticky feel. Of the several polymers available, polyvinylpyrrolidone (more popularly termed PVP) is outstanding and currently employed in aerosol hair grooming preparations. When a PVP alcohol solution is applied in an aerosol system to human hair under a relative humidity of less than 50%, the tendency of the resulting film to tackiness is substantially decreased. As a result thereof the prep- .aration is acceptable by all consumers. However, when the relative humidity is above 50%, and particularly at humid atmospheres, films of PVP, sprayed from an aero sol system, pick up considerable moisture. The moisture is retained and results in a tacky film. In view of this property, the aerosol preparation is extremely undesirable Where a dry hair condition is required as is the case with most users, especially women, the equilibrium water content of PVP depends upon the relative humidity of the atmosphere. The moisture content varies in a linear fashion with relative humidity, and the equilibrium percentage of moisture is about one-third of the relative humidity. Thus, if PVP is exposed to a relative humidity of 5 0%, the moisture pickup is approximately onethird of the relative humidity and therefore the resulting film contains about 17% moisture. To overcome the unique hygroscopicity of PVP, it has been suggested to employ detackifying agents such as shellac, cellulose acetate-propionate, etc. The former yields films which become opaque at high humidities, and the latter yields a film insoluble in ethyl alcohol. Carboxy-methylcellulose, cellulose acetate, methyl methacrylate polymer, polyvinyl formal, etc., are not effiective as detacki-fiers under conditions of extremely high humidities.

It is an object of the present invention to provide an improved non-alcoholic film forming composition particularly adaptable for hair waving, hair setting and hair dressing compositions free from the foregoing disadvantages and which, in addition, possess new and desirable properties.

Other objects and advantages will become apparent from the following description.

I have found that a composition possessing new and desirable properties for the formation of films and particularly for application to human hair comprises a solution of a copolymer of N-vinylpyrrolidone and a vinyl ester in trifluoroethyl chloride (CF CH Cl). Such solution when sprayed on any surface and particularly when applied to human hair yields a glossy film which is substantially tack-free under normal conditions of relative humidity. The resulting film when exposed to a relative humidity of 50% and higher contains no more than 10% moisture and is sufficiently water sensitive so that it can be removed from any surface, including hair, by a simple water washing. In view of this unique property of the copolymer in solution in the trifluoroethyl chloride, it is not necessary to employ detackifying agents.

I have further found that in order to achieve the following desirable properties, it is necessary to employ from 30-60% by weight of a vinylpyrrolidone monomer and from 40-70% by weight of a monomeric vinyl ester. When such weight-percentage ratios are employed in preparing the copolymer, films resulting therefrom maintain sufiicient water-sensitivity so that they can be removed from the hair. A copolymer of 70% by weight of N- vinylpyrrolidone and 30% by weight of a vinyl ester When exposed to a relative humidity of 50% contains no more than 10% moisture. At the same humidity, a 50-50 copolymer contains no more than 6% moisture and a copolymer of 30% by weight of N-vinyl-pyrrolidone and 70% by weight of a vinyl ester contains no more than 3% moisture. The copolymers in such ratios are soluble in trifluoroethyl chloride. The ratio of polymerizable monomers used may range widely to yield water-sensitive to water-insoluble copolymers, both of which are soluble in trifluoroethyl chloride. For hair grooming preparations I prefer to employ copolymers in which monomers are in the ratio of 30:60 of the N-vinylp-yrrolidone and 40:70% by weight of the vinyl ester. tions a copolymer is obtained which is readily soluble in trifluoroethyl chloride to yield an aerosol hair grooming preparation, the films of which do not become opaque In these proporor tacky at high humidities. The resulting films are glossy, tack-free and readily removed by a water wash or a. water rinse.

As illustrative examples of N-vinylpyrro'lidones which may be copolymerized in the aforestated concentrations with a vinyl ester, the following may be mentioned:

As illustrative examples of; polymerizable vinyl esters, the following may be mentioned:

Vinyl acetate Vinyl lglyeolate Vinyl chloride Vinyl formate Vinyl propionate Vinyl butyrate Vinyl stear-ate The copolymers, prepared with the aforementioned monomersas herein described, correspond to a range of Fikentscher K value of 10 to 90. These values apply to both the water-sensitive and water-soluble copolymers. K. value as used herein is defined by the following implicit function of Fikentscher, Cellulosechemie, 13, 60 (1932) 0.001K-l-O.OO0075K Relative VISCOSllJ) -10C 1+0 0015KC A definition of K value is also given in Modern Plastics, 23, 157-161 (Nov. 1945').

The invention will be described in greater length in conjunction with the following examples. It is to be understood, however, that these examples are merely illustrative and are not intended that the scope of the invention be limited to them and to the details set forth he i EXAMPLE I A one-liter, three-necked flask equipped with stirrer, reflux condenser and a thermometer was charged with 75, grams of vinyl acetate, distilled, 225 grams'of N vinyl- Z-pyrrolidone, distilled, and 300 ml. of Z-butanone. The flask was heated to 75 C. with stirring for 5 minutes. After 5 minutes, 3 grams of 2,2'-azodiisobutyronitrile dissolved in 37.5 ml. of Z-butanone was added to the flask. The flask was stirred and maintained at 70 C. for a total of 12 hours. The product was recovered by evaporating the Z-butanone leaving a solid, white, clear polymer containing 75% N-vinyl-Z-pyrrolidone and 25% vinyl acetate. The polymer dissolved in 2-butanonegave a Eikentscher Kvalue of 17.

EXAMPLE n A two-liter, three-necked, groundjoint, Pyrex flask equipped with two Allihn condensers, mechanical stirrer with halt-moon blade, thermometer, and a nitrogen inlet tube was charged with 139.0 grams, (175 ml.)- of denatured ethanol, 83.25 grams (0.75 mole) (80 ml.) of distilled N-vinyl-Z-pyrrolidone, 64.57 grams (0.75 mole) (69.3 ml.) of vinyl acetate, distilled, and 0.75- gram of Z'-=, @Q 1 iS0b1, tynonitrile dissolved in 30 ml. of denatured ethanol. The flask was flushed with nitrogen and the inlet rate adjusted to about 30-60 bubbles per minute. The flask was heated on a steam bath of 70 C. The steam was turned oil and the catalyst was added via the condenser. The temperature dropped to 56 C. The steam was then connected, and. the flask heated to the reflux temperature (ca. 76 C.). Heating and stirring were continued for 12 hours. Part of the product dissolved in the ethanol was transferred to a tared Pyrex dish. The dish was placed in front of an electric fan for 36 hours to evaporate the alcohol. Some of the solution was used as a 50% solid ethanol solution. The product when corrected for volatiles weighed 131.6 grams or gave an 89.2% yield. Analysis of the product for nitrogen gave 7.31% which when corrected indicates 60% bound-vinyl-2-pyrrolidone and 40% hound vinyl acetate by dilierence. Analysis for volatiles gave 4.6%. Analysis for free monomer gave 0.01% calculated as N-. vinyl-Z-pyrrolidone.

EXAMPLE I11 Into an Autoclave Engineer steel autoclave were placed 73.80 grams of N-vinyl-Z-pyrrolindone, 20.80 grams of vinyl chloride, 87.5 grams of Z-butanone and 0.410 gram of 2,2-azodiisobutyronitrile catalyst. The autoclave was sealed and heated to 60 C. and stirred with an enamel coated stirrer for 20 hours. The autoclave was cooled to room temperature and vented into a Dry Ice trap. The trap did not gain in weight. The contents of the autoclave were poured into a tared Pyrex dish and placed in an air stream to evaporate the solvent. After 18 hours a thick syrup remained. The thick syrup was placed in a desiccator under vacuum and the remaining solvent removed. The polymer obtained was a straw colored, friable material which was easily pulverized with mortar and pestle. Analysis for volatiles indicated that the actual yield of dry polymer was-93% of the theoretical yield. Analysis for the N content bound in the polymer indicated 90% N-vinyl-Z-pyrrolidone content and 10% vinyl chloride content by diflerence. The polymer gave a Fikentscher K value of 22 in water.

EXAMPLE IV EXAMPLE V Into av metal aerosol can, partially submerged in asolid carbon dioxide/ acetone bath, were condensed 20 grams of trifluoroethyl chloride. To this was added" 0.6 gram of N-vinyl-2-pyrrolidone/vinyl chloride copolymer of Example A nozzle and valve assembly was attached to the can and the entire assembly was held together in a brass cage. The can was checked forleaks by submerging in water. The aerosol sprayer was allowed to warm to room temperature. Glass panels were sprayed. 'Ihe films dried almost immediately to odor-free, clear films. The films were not tacky.

EXAMPLE VI Into a threenecked, one-liter Pyrex flask equipped with an Allihn condenser, a thermometer, a mechanical stirrer, and a nitrogen inlet was charged 60.0 grams of distilled N-vinyl-Z-pyurolidone, 40.0 grams of distilled vinyl propionate and 200 grams of anhydrous ethanol. The flask was flushed with nitrogen and the inlet rate of the gas adjusted to about 30 bubbles per minute. The flask was heated and stirred for 30'minutes to 60 C. At this point 0.1 gram of 2,2'-azodiisobutyronitrile was added as the catalyst. The flask was maintained at C. and was stirred for a total of 12 hours. At this point the reaction mixture gave an analysis of 3% residual unsaturation.

0.1 gram of 2,2'-azodiisobutyronitrile was added and the flask was heated for an additional 3 hours. The prodnot was recovered for A of the reaction mixture by vacuum stripping. The product consisted of a white, friable, transparent polymer. The remaining half of the reaction solution was bottled for use in its original condition.

Analysis indicated the polymer contained 60% vinylpyrrolidone and 40% vinyl propionate. A sample of the dried polymer gave a Fikentscher K value of 33 in 2- butanone.

Into a metal aerosol can, partially submerged in a solid carbon dioxide/ acetone bath, were condensed 20 grams of trifluoroethyl chloride. To this was added 0.6- gram of the dried copolymer prepared as above. A nozzle and valve assembly was attached to the can and the entire assembly was held together in a brass cage. The can was checked for leaks by submerging in water. The aerosol sprayer was allowed to warm to room temperature. Glass panels were sprayed. The films dried almost immediately to odor-free, clear films. The films were not tacky.

EXAMPLE VII Into a three-necked flask equipped with an Allihn condenser, a thermometer, a nitrogen inlet, and a mechanical stirrer was charged 55.0 grams of N-vinyl-Z-pyrrolidone, 45.0 grams of vinyl propionate and 200 grams of 2- butanone. The flask was flushed with nitrogen and the in let rate of the gas was adjusted to about 30 bubbles per minute. The flask was stirred and heated to 60 C for 30 minutes. At this point 0.1 gram of 2,2'-azodiiso|butyronitrile was added as the catalyst. The flask was stirred and maintained at 30 C. for a total of 12 hours. The polymer was recovered from the reaction solution by drying in a vacuum desiccator for 24 hours at less than 0.2 mm. of mercury vacuum.

The white, brittle, translucent polymer was analyzed and the analysis indicated that it contained 55% vinylpyrrolidone and 45% vinyl propionate. A sample of the dried polymer gave a Fikentscher K value of 30 in 2- butanone.

Into a metal aerosol can, partially submerged in a solid carbon dioxide/ acetone bath, were condensed 20 grams of trifiuoroethyl chloride. To this was added 0.6 gm. of the dried copolymer prepared as above. A nozzle and valve assembly was attached to the can and the entire assembly was held together in a brass cage. The can was checked for leaks by submerging in Water. The aerosol sprayer was allowed to warm to room temperature. Glass panels were sprayed. The films dried almost immediately to odor-free, clear films. The films were not tacky.

In order to ascertain the criticality of the weight-percent ratio of the monomers in the copolymer, several copolyers were made in which the N-vinyl-2-pyrrolidone content ranged from 20 to 60% by weight. Films of such copolymers were both air-dried and heated and their dissolving tendencies in water observed. The results obtained are shown in the following table:

Comparison of VP/ VA Copolymers Films immersed in water, air-dried films VIP/VA} weight percent ratio Time for film to release from glass slide, min.

Water solubility 3 Soluble. Do.

Do. Partly sol.

Do. Not dispersible.

6 by requiring several vigorous washings before removal. In other words, the desired ratio in which all of the aforementioned desired properties are found is in 30 to 60% by weight Nvinyl-2-pyrrolidone and from 40 to 70% by weight of vinyl ester.

This application is a continuation-impart of pending application, Serial No. 621,206, filed on November 9, 1956.

I claim:

1. A non-alcoholic sprayable film forming preparation consisting essentially of a copolymer of 30-70% by weight of N-vinylpyrrolidone and 70-30% by weight of a vinyl ester in solution of trifiuorethyl chloride (OF CH CI), said ester selected from the class consisting of vinyl acetate, vinyl glycolate, vinyl chloride, vinyl formate, vinyl propionate, vinyl butyrate and vinyl stearate.

2. A non-alcoholic hair grooming preparation consisting essentially of a copolymer of 3060% by Weight of N-vinylpyrrolidone and 40-70% by weight of a vinyl ester in solution of trifluorocthyl chloride (CF CH Cl) serving both as solvent and aerosol propellant, said ester selected from the class consisting of vinyl acetate, vinyl glycolate, vinyl chloride, vinyl formate, vinyl propionate, vinyl butyrate and vinyl stearate.

3. A non-alcoholic sprayable film forming preparation substantially tack-free under normal conditions of relative humidity consisting essentially of a copolymyer of 50% by weight of N-vinylpyrrolidone and 50% by weight of a vinyl ester in solution of trifluorocthyl chloride (CF CH Cl) which serves both as solvent and aerosol propellant, said ester selected from the class consisting of vinyl acetate, vinyl glycolate, vinyl chloride, vinyl formate, vinyl propionate, vinyl butyrate and vinyl stearate.

4. A non-alcoholic sprayable film forming preparation substantially tack-free under normal conditions of relative humidity consisting essentially of a copolymer of 30% by weight of N-vinylpyrrolidone and 70% by Weight of a vinyl ester in solution of trifluoroethyl chloride (CF CH CI) which serves both as solvent and aerosol propellant, said ester selected from the class consisting of vinyl acetate, vinyl glycolate, vinyl chloride, vinyl formuate, vinyl propionate, vinyl butyrate and vinyl stearate.

5. A non-alcoholic sprayable film forming preparation consisting essentially of a copolymer of 10-50% by weight of a vinyl ester and 50-90% by weight of N-vinylpyrrolidone in solution of trifluoroethyl chloride (CF CH CU which serves both as solvent and aerosol propellant, said ester selected from the class consisting of vinyl acetate, vinyl glycolate, vinyl chloride, vinyl formate, vinyl propionate, vinyl butyrate and vinyl stearate.

References Cited in the file of this patent UNITED STATES PATENTS Midgley et al. Sept. 12, 1933 Benning Feb. 4, 1941 Miller Feb. 16, 1954 OTHER REFERENCES 

1. A NON-ALCOHOLIC SPRAYABLE FILM FORMING PREPARATION CONSISTING ESSENTIALLY OF A COPOLYMER OF 30-70% BY WEIGHT OF N-VINYLPYRROLIDONE AND 70-30% BYE WEIGHT OF A VINYL ESTER IN SOLUTION OF TRIFLUORETHYL CHLORIDE (CF2CH2CI), SAID ESTER SELECTED FROM THE CLASS CONSISTING OF VINYL ACETATE, VINYL GLYCOLATE, VINYL CHLORIDE, VINYL FORMATE, VINYL PROPIONATE, VINYL BUTYRATE AND VINYL STEARATE. 